CN104220537A - Printing ink, apparatus and method - Google Patents

Printing ink, apparatus and method Download PDF

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Publication number
CN104220537A
CN104220537A CN201080045759.1A CN201080045759A CN104220537A CN 104220537 A CN104220537 A CN 104220537A CN 201080045759 A CN201080045759 A CN 201080045759A CN 104220537 A CN104220537 A CN 104220537A
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CN
China
Prior art keywords
ink
weight
lamp
solvent
radiation curable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201080045759.1A
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Chinese (zh)
Inventor
R·A·法萨姆
N·古尔德
J·沃德
B·麦格雷戈
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sericol Ltd
Original Assignee
Sericol Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0914648A external-priority patent/GB0914648D0/en
Priority claimed from GB0914652A external-priority patent/GB0914652D0/en
Priority claimed from GB0920271A external-priority patent/GB0920271D0/en
Application filed by Sericol Ltd filed Critical Sericol Ltd
Publication of CN104220537A publication Critical patent/CN104220537A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
    • B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • B41J11/0024—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using conduction means, e.g. by using a heated platen
    • B41J11/00244—Means for heating the copy materials before or during printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat

Abstract

The present invention provides an inkjet ink comprising at least 30 % by weight of organic solvent based on the total weight of the ink, a radiation curable material, a photoinitiator and optionally a colourant. The invention also provides an apparatus for printing the ink wherein the apparatus comprises at least one printhead, a means for evaporating solvent from the printed ink and a source of actinic radiation. Furthermore, the invention provides a method of inkjet printing comprisingi) inkjet printing the inkjet ink as defined above on to a substrate; ii)evaporating at least a portion of the solvent from the printed ink; and iii)exposing the printed ink to actinic radiation to cure the radiation curable material.

Description

Printing-ink, equipment and method
The present invention relates to printing-ink, printing equipment and printing process.Especially, the present invention relates to jetted ink, ink-jet printing apparatus and ink jet printing method.
Compare with silk screen printing with conventional art such as lithography, due to its low implementation cost and versatility, Digital ink jet printing is becoming the manufacture method of the meticulous printed images for advertisement of increased popularity.Ink-jet printer comprises one or more printhead, and it comprises series of spray nozzles, is ejected on base material by ink by nozzle.Printhead is arranged in printer carriage usually, and in print procedure, printer carriage moves around (moving around on base material) along printer width.
Use the ink chemistry that two kinds main: by the ink of evaporating solvent drying with by exposing dry ink under uv irradiating to the open air.The solvent-based ink-jet printer of wide format is the approach entering the sector economy, because compared with solidifying with UV the more complicated machine that uses, they are selections of relatively low cost.Solvent-based ink-jet printing also has other advantage.Except cost is lower, obtained ink film thinner (therefore soft) and produce the quality with gloss finish good seem natural image.And due to the high viscosity of ink, be difficult to realize very high pigment load: if add too many pigment in UV curing inks, ink becomes too sticky and can not be injected.On the contrary, solvent-based ink comprises a high proportion of solvent, therefore has lower viscosity, this means to allow higher pigment load.In addition, the printing film produced by solventbased inkjet ink is formed primarily of other solid be included in ink of pigment and relatively small amount.Therefore pigment not crested substantially, produces strong, lively and distinct color and large colour gamut.
But solvent-based ink-jet technology has some limitation.Especially, solvent-based ink can not stick on the base material of some type, especially non-porous substrate such as plastics, and the film poor solvent resistance after solidification.
Therefore the jetted ink substituted and the printing equipment that can print this ink is needed.
For this reason, the invention provides a kind of jetted ink, comprise based on the organic solvent of total weight at least 30 % by weight, radiation curable material, light trigger and optional tinting material.
Present invention also offers a kind of equipment for printing solvent based ink jet inks, comprise at least one printhead, for the device of evaporating solvent from printing-ink and actinic radiation source.
Present invention also offers a kind of method using equipment printing as defined above jetted ink as defined above, the method comprises:
Ink is ejected into base material from printhead;
Solvent is at least partially evaporated from printing-ink; With
Printing-ink is exposed to the open air under actinic irradiation solidify radiation curable material.
Now with reference to accompanying drawing, the present invention is described, wherein:
Fig. 1 shows the skeleton view of the exemplary according to ink-jet printing apparatus of the present invention; With
Fig. 2 shows the sectional view of the exemplary according to ink-jet printing apparatus of the present invention.
The spectrum that Fig. 3 shows the amalgam vapour lamp compared with conventional low mercury lamp exports.
Fig. 4 shows the sectional view of the low pressure mercury lamp that reflectance coating is housed.
ink
Ink of the present invention comprises modification ink adhesive composition.In ink, the existence of radiation curable material and light trigger means and to be formed crosslinked in the ink film of drying, causes improving with the adhesive power of the base material of certain limit and solvent resistance.But the organic solvent having at least 30 % by weight means the favourable performance estimating to maintain solventbased inkjet ink.
" radiation curable material " refers in the presence of photoinitiators, is polymerized or crosslinked material when irradiating and exposing to the open air under (normally UV-light).
Described radiation curable material can comprise monomer, oligopolymer or their mixture that molecular weight is 450 or less.This monomer and/or oligopolymer can have functionality in various degree, can use the monomer that comprises single functionality, difunctionality, three-functionality-degree and higher functional degree and or the mixture of combination of oligopolymer.
Preferably, described radiation curable material comprises radiation curable oligopolymer.
Be applicable to radiation curable oligopolymer of the present invention and comprise main chain, such as polyester backbone, polyurethane backbone, epoxy main chains or polyether backbone, and one or more irradiation polymerizable groups.Any group that described polymerizable groups can be polymerized when can be and expose to the open air under irradiation.
The molecular weight of preferred oligopolymer is 500-4000, more preferably 600-4000.If the structure of known oligopolymer can calculate molecular weight or molecular weight can use polystyrene standards to measure with gel permeation chromatography.Therefore, for polymeric material, number-average molecular weight can obtain by gel permeation chromatography and polystyrene standards.
In one embodiment, described radiation curable material is polymerized by Raolical polymerizable.
Suitable free radical polymerizable monomer is well known in the art, and comprises (methyl) acrylate, α, beta-unsaturated ether, vinylamide and their mixture.
Simple function (methyl) acrylate monomer is well known in the art, preferably acrylate.Preferred example comprises acrylate (PEA), ring trimethylolpropane formal acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofuran (THF) acrylate (THFA), 2-(2-ethoxy ethoxy) ethyl propylene acid esters, octadecyl acrylate (ODA), methacrylic acid 13 ester (TDA), isodecyl acrylate (IDA) and lauryl acrylate.Particularly preferably PEA.
Suitable multifunctional (methyl) acrylate monomer comprises difunctionality, trifunctional and four functional monomers.The example that can be included in the polyfunctional acrylate monomer in described jetted ink comprises hexanediol diacrylate, three vinylformic acid trishydroxymethyl propyl ester, pentaerythritol triacrylate, diacrylate macrogol ester (such as diacrylate Tetraglycol 99 ester), dipropylene glycol diacrylate, tripropylene glycol diacrylate, diacrylic acid pentyl diol ester, the acrylate of two (tetramethylolmethane) ester of six vinylformic acid and ethoxylation or propoxylation ethylene glycol or polyvalent alcohol, the diacrylate of such as ethoxylated neopentylglycol, the triacrylate of ethoxylated trimethylolpropane and their mixture.
Suitable multifunctional (methyl) acrylate monomer also comprises the ester (i.e. methacrylic ester) of methacrylic acid, such as dimethacrylate hexylene glycol ester, trimethacrylate acid trishydroxymethyl propyl ester, TEGDMA, diethyleneglycol dimethacrylate(DEGDMA), Ethylene glycol dimethacrylate, dimethacrylate BDO ester.Also the mixture of (methyl) acrylate can be used.
(methyl) acrylate will have its standard implication herein, i.e. acrylate and/or methacrylic ester.Simple function and multifunctionally also will have their standard implication, participates in one and two or more groups of polyreaction when being namely solidification respectively.
When being combined with one or more (methyl) acrylate monomers, α, beta-unsaturated ether monomer can be polymerized by Raolical polymerizable and can be used for reducing ink viscosity.Example is well-known in the art, comprises vinyl ethers such as triethyleneglycol divinylether, diethylene glycol divinyl ether, Isosorbide-5-Nitrae ,-cyclohexanedimethanol divinyl base ether and ethylene glycol mono vinyl ether.α can be used, the mixture of beta-unsaturated ether monomer.
N-vinylamide and N-(methyl) acrylamide also may be used in ink of the present invention.N-vinylamide is monomer well-known in the art, does not therefore need to describe in detail.N-vinylamide has the vinyl be connected with the nitrogen-atoms in amide group, and it can be substituted by (methyl) acrylate monomer in a similar fashion further.Preferred example is N-caprolactam (NVC) and NVP (NVP).Similarly, N acrylamide is also well-known in the art.N acrylamide also has the vinyl be connected with amide group, but by being connected with the carbon atom in carbonyl, and again can be substituted by (methyl) acrylate monomer in a similar fashion further.Preferred example is N-acryloyl morpholine (ACMO).
Particularly preferred radiation curable material has free redical polymerization group, the oligopolymer that preferably (methyl) is acrylate-based.Most preferably acrylate functional oligomer's thing.
In one embodiment, described oligopolymer comprises two or more free redical polymerization groups, preferably more than three or three, more preferably four or more.Particularly preferably comprise the oligopolymer of six polymerizable groups.
Described oligopolymer preferably comprises polyurethane backbone.
Particularly preferred radiation curable material is urethane acrylate oligomer, because they have excellent adhesive power and elongation.The most preferably urethane acrylate of three-functionality-degree, four functionality, five functionality, six functionality or higher functional degree, particularly six functionality urethane acrylates, the film that they produce has good solvent resistance.
The example of other suitable radiation curable oligopolymer comprises epoxy-based material, such as bisphenol A epoxy acrylate and epoxy novolac acrylates, and they have curing speed and provide the cured film with good solvent resistance fast.
In the presence of photoinitiators, when exposing to the open air under irradiation, the radiation curable oligopolymer used in the preferred ink of the present invention solidify to form crosslinked solid film.Gained film and base material have good adhesive power and have good solvent resistance.And any radiation curable oligopolymer that can solidify to form crosslinked solid thin-film compatible with remaining ink component is applicable in ink of the present invention.Therefore, ink formulations Designers can select from oligopolymer suitable on a large scale.Especially, oligopolymer can be the low molecular weight material for liquid form at 25 DEG C.When object is production low viscosity ink, this is useful.And, so when preparing ink, use lower molecular weight, liquid-state oligomers are favourable, because lower molecular weight liquid-state oligomers probably dissolves in the solvent of wide region.
Be 0.5-20Pa.s for preferred oligopolymer of the present invention viscosity at 60 DEG C, being more preferably 5-15Pa.s at 60 DEG C, is most preferably 5-10Pa.s at 60 DEG C.Oligomer viscosities can use the ARG2 rheometry of T.A. instrument manufacturing, and the 40mm oblique line/2 ° steel pricker at it uses 60 DEG C, shearing rate is 25 seconds -1.
In one embodiment, based on the free radical curable materials gross weight existed in ink, described radiation curable material comprises 50-100 % by weight or 75-100 % by weight free radical curable oligomers and 0-50 % by weight or 0-25 % by weight free radical curable monomer.
Preferably, based on total weight, described ink comprises (methyl) acrylate that the molecular weight that is less than 20 % by weight is less than 450, or is less than 10 % by weight, is more preferably less than 5 % by weight.In an especially preferred embodiment, ink of the present invention is substantially devoid of (methyl) acrylate that molecular weight is less than 450.
In an embodiment, based on total weight, ink comprises (methyl) acrylate that the molecular weight that is less than 20 % by weight is less than 600, or is less than 10 % by weight, is more preferably less than 5 % by weight.In an especially preferred embodiment, ink of the present invention is not substantially containing (methyl) acrylate that molecular weight is less than 600.
" be substantially devoid of " and refer to that (methyl) acrylate not having molecular weight to be less than 450 or 600 is on purpose added in ink respectively.But, (methyl) acrylate that a small amount of molecular weight is less than 450 or 600 can be tolerated respectively, such as, may be present in those of the radiation curable oligopolymer be purchased as impurity.
In the embodiment that the present invention one is alternative, described radiation curable material can be polymerized by cationic polymerization.Suitable material comprises trimethylene oxide, cycloaliphatic epoxides, bisphenol A epoxide, epoxy novolac etc.The mixture of cationization curable monomer and oligopolymer can be comprised according to the radiation curable material of this embodiment.Such as radiation curable material can comprise the mixture of epoxy oligomer and oxetane monomer.
In one embodiment, based on the gross weight of the radiation curable material existed in ink, described radiation curable material comprises 0-40 % by weight cationization curable oligomers and 60-100 % by weight cationization curable monomer.
Described radiation curable material can also comprise the composition of the material of free redical polymerization and cationically polymerizable.
Based on the gross weight of ink, the amount of the radiation curable material preferably existed in composition is 2 % by weight to 65 % by weight, is more preferably 2-45 % by weight, is more preferably 5-35 % by weight, be more preferably 8-25 % by weight, most preferably be 10 % by weight to 25 % by weight.
Ink of the present invention comprises one or more light triggers.When ink of the present invention comprises the material of free redical polymerization, photoinitiator system comprises free radical photo-initiation, and when described ink comprises the material of cationically polymerizable, photoinitiator system comprises cation light initiator.When described ink comprises the composition of the material of free redical polymerization and cationically polymerizable, need radical initiator and cationic initiator.
Free radical photo-initiation can be selected from any one in those known in the art.Such as; benzophenone, 1-hydroxy cyclohexyl phenylketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-benzyl-2-dimethylamino-(4-morpholinyl phenyl)-butane-1-ketone, isopropyl thioxanthone, benzoin dimethylether, two (2; 6-dimethylbenzoyl)-2; 4,4-trimethylphenylphosphine oxide and their mixture.These light triggers are known and are commercially available, such as, with trade(brand)name Irgacure and Darocur (purchased from Ciba) and Lucerin (purchased from BASF).
When cationization curable system, the cationic initiator of any appropriate can be used, such as sulphur or iodine type system.Limiting examples comprises the Rhodorsil PI 2074 purchased from Rhodia; Purchased from MC AA, MC BB, MC CC, MC CC PF, the MC SD of Siber Hegner; Purchased from the UV9380c of Alfa Chemicals; Uvacure 1590 purchased from UCB Chemicals and the Esacure 1064 purchased from Lambertis pa.
Preferably, based on the gross weight of ink, the amount of initiator is 1-20 % by weight, preferred 4-10 % by weight.
Ink of the present invention comprises organic solvent.This organic solvent is at room temperature liquid form and can be left the carrier of component as ink.The organic solvent constituent of ink of the present invention can be the mixture of single solvent or two or more solvent.As known solventbased inkjet ink, in order to make ink setting, needing from printing-ink, evaporate the organic solvent used in ink of the present invention, usually adopting the mode of heating.Described solvent can be selected from any solvent conventional in printing industry, such as glycol ethers, glycol ether-ether, alcohols, ketone, ester class and pyrrolidone.
Based on the gross weight of ink, the amount of organic solvent preferably at least 40 % by weight, more preferably at least 45 % by weight, and more preferably at least 50 % by weight, such as 50-85 % by weight or 50 % by weight to 80 % by weight.In an especially preferred embodiment, based on the gross weight of ink, the amount of organic solvent is at least 55 % by weight, such as 60-85% or 60 % by weight to 75 % by weight.
Only dry known solventbased inkjet ink and crosslinked or polymerization does not occur is evaporated by solvent.Therefore the film produced has limited chemical resistance.In order to improve the tolerance of the common solvent such as alcohols and gasoline of printed matter, the adhesive material that solubleness is limited in these solvents is added in this ink.This tackiness agent normally solid form at 25 DEG C, like this when solvent volatilizees from ink, produces solid print film.Suitable tackiness agent is the poor solubility of vinyl chloride copolymer resin usually in all solvents such as glycol ether acetates and pimelinketone except most strong solvent such as, glycol ether acetates ester and pimelinketone are all listed in " harmful " and there is strong smell.In order to dissolved adhesive, generally these solvents are added in ink.
The radiation curable material that ink of the present invention solidifies when comprising ink setting, does not therefore need to make printing film have the solvent resistance of improvement and comprises tackiness agent at ink.Therefore, in one embodiment of the invention, without the need for machine dissolution with solvents tackiness agent such as vinyl chloride copolymer resin, this means that ink formulations Designers has more freedom when selecting suitable solvent or solvent mixture.
In a preferred embodiment, organic solvent is hypotoxicity and/or low smell solvent.Also preferably Environmental Protection Agency or Council of Europe give the VOC solvent exempting status.
Most preferred solvent is selected from glycol ethers and organic carbonate class and their mixture.The particularly preferably mixture of cyclic carbonate ester such as propylene carbonate and propylene carbonate and one or more glycol ethers.
Preferred replace solvents comprises lactone, has been found that it improves the adhesive power of ink and PVC base.Particularly preferably lactone and the mixture of one or more glycol ethers and the mixture of lactone, one or more glycol ethers and one or more organic carbonates.Particularly preferably gamma-butyrolactone and the mixture of one or more glycol ethers and the mixture of gamma-butyrolactone, one or more glycol ethers and propylene carbonate.
In another embodiment of the invention, dibasic ester and/or biological solutions can be used.
The solvent that dibasic ester is known in the art.They can be described to two (C of the representative examples of saturated aliphatic diprotic acid of 3-8 the carbon atom with following general formula 1-C 4alkyl) ester:
Wherein A represents (CH 2) 1-6, R 1and R 2can be identical or different and represent C 1-C 4alkyl, they can be the alkyl diradicals of 1-4 carbon atom of straight chain or side chain, preferable methyl or ethyl, most preferable.The mixture of dibasic ester can be used.
Biological solutions or have from the solvent replacements of Biological resources significantly reduces the potentiality of the VOC amount of the contaminate environment of discharging into the atmosphere, and the continuable further advantage had.And have been found that the new production process of the biological solutions derived from biological raw material, it makes, and biological solutions production cost is lower, purity is higher.
The example of biological solutions comprises soybean methyl ester, lactate, poly-hydroxyl alkane ester, terpene and non-linear alcohol and D-limonene.Soybean methyl ester is obtained by soybean.Fatty acid ester is prepared by the esterification of soybean oil and methyl alcohol.Lactate preferably uses the lactic acid that obtains of fermenting, and it and methyl alcohol and/or ethanol synthesis prepare ester.An example is ethyl lactate, and it is derived from corn (renewable resources) and by FDA approval as foodstuff additive.Poly-hydroxyl alkane ester to be fermented the linear polyesters obtained by sugar or lipid.Terpene and non-linear alcohol can derived from corn ear/rice husks.An example is the D-limonene can extracted from citrus peel.
Other solvent can be comprised in organic solvent constituent.The mode that other solvent of special frequent origins introduces ink jet ink formulations with tinting material obtains.Tinting material is prepared with the form of dispersible pigment dispersion in solvent such as 2-ethylhexyl usually.Based on the gross weight of dispersible pigment dispersion, solvent often about 40-50 % by weight and dispersible pigment dispersion accounts for the 5-15 % by weight of ink usually, sometimes more.
Described ink is preferably substantially free of water, although some moisture usually can be absorbed by ink or be present in the component of ink as impurity from air, such degree is allowed.Such as, based on the gross weight of ink, ink can comprise the water being less than 5 % by weight, is preferably less than the water of 2 % by weight, is most preferably less than the water of 1 % by weight.
Ink of the present invention can be colored ink or colorless ink.
" colourless " refers to that ink is substantially devoid of tinting material and makes naked eyes not find color.But, can allow that naked eyes can be found to but not colorific a small amount of tinting material.Based on total weight, the amount of tinting material can be less than 0.3 % by weight usually, is preferably less than 0.1 % by weight, is more preferably less than 0.03 % by weight.Colorless ink also can be described to " transparent " or " water white transparency ".
Colored ink of the present invention comprises at least one tinting material.Described tinting material can be dissolved or dispersed in the liquid medium of ink.Described tinting material preferably dispersibles pigment, it is type known in the art and is commercially available, such as, with trade(brand)name Paliotol (purchased from BASF plc), Cinquasia, Irgalite (all purchased from Ciba Speciality Chemicals) and Hostaperm (purchased from Clariant UK).Pigment can be color required arbitrarily, such as pigment yellow 13, pigment yellow 83, Pigment Red 9, Pigment red 184, pigment Blue 15: 3, pigment Green 7, pigment violet 19, Pigment black 7.Black and three-color (halftone) block method printing required color are useful especially.The mixture of pigment can be used.
In one aspect of the invention, preferred following pigment.Cyan: phthalocyanine pigment, such as phthalocyanine blue 15.4.Yellow: azo pigment, such as pigment Yellow 12 0, Pigment Yellow 73 151 and Pigment Yellow 73 155.Magenta: quinacridone pigment, crystallization quinacridone such as the Cromophtal Jet magenta 2BC and Cinquasia RT-355D of such as pigment violet 19 or mixing.Black: charcoal blacks, such as Pigment black 7.
Be dispersed in granules of pigments in ink should the enough little ink that makes by inkjet nozzle, usual particle diameter is less than 8 μm, is preferably less than 5 μm, is more preferably less than 1 μm, is particularly preferably less than 0.5 μm.
Based on the gross weight of ink, the amount of tinting material is preferably 20 % by weight or less, and preferably 10 % by weight or less, more preferably 8 % by weight or less, most preferably 2-5 % by weight.But white ink may need the pigment of greater concn, such as, based on the gross weight of ink, up to and comprise 30 % by weight or 25 % by weight.
Described ink optionally can contain thermoplastic resin.Described thermoplastic resin exposes the reactive group that can be cross-linked to the open air not included under irradiation.In other words, thermoplastic resin is not radiation curable material.It is 10,000-100 that the molecular weight ranges polystyrene standards of suitable material is measured by GPC, 000.Described thermoplastic resin can be selected from such as epoxy resin, vibrin, Vinylite or (methyl) acrylate resin.Preferred methacrylate multipolymer.When it is present, based on the gross weight of ink, described ink can comprise the thermoplastic resin of 1-5 % by weight.Described thermoplastic resin adds the viscosity of ink film before curing, causes print distinctness to improve.Described thermoplastic resin also reduces the second-order transition temperature of the rear ink of solidification, gives the thin film flexible that application examples is as higher in vehicular sideview application.
In one embodiment, based on the gross weight of ink, ink of the present invention comprises the organic solvent of at least 50 % by weight; Radiation curable material, wherein, based on the gross weight of the radiation curable material existed in ink, the molecular weight that described radiation curable material comprises 50-100 % by weight to be the free radical curable oligomers of 600-4000 and the molecular weight of 0-50 % by weight be 450 or less free radical curable monomer; Free radical photo-initiation and optional tinting material.
Described jetted ink shows required low viscosity (at 25 DEG C, 200mPa.s or less, preferred 100mPa.s or less, more preferably 25mPa.s or less, more preferably 10mPa.s or less, most preferably 7mPa.s or less).
In order to produce high-quality printed images, need little liquid droplets size.And compared with larger drop size, the surface-area of small droplets is higher, this is conducive to evaporating solvent from the ink sprayed.Therefore small drop sizes has advantage in rate of drying.Preferably rise following drop size with 50 skins jetted ink of the present invention is sprayed, below preferably 30 skins rise, below more preferably 10 skins rise.
In order to realize and 50 skins can be of a size of rise or the consistency of less printhead by liquid droplets, need low viscous ink.Preferably at 25 DEG C, viscosity is 10mPa.s or less, such as 2-10mPa.s, 4-8mPa.s or 5-7mPa.s.Because the viscosity ratio of the acrylate monomer that uses in composition and oligopolymer is higher, it is problematic for using conventional radiation curable ink to reach these low viscosity, but there is a considerable amount of organic solvent in ink of the present invention makes these low viscosity be achieved.
Ink viscosity can use the Brookfield viscometer that thermostatic control cup and specific gravity hydrometer are housed to record, such as, specific gravity hydrometer 00 is housed at 25 DEG C with the DV1 low viscosity viscometer that 20rpm runs.
Other component of type known in the art may reside in ink with improving SNR or function.These components can be, the synergistic agent of such as tensio-active agent, defoamer, dispersion agent, light trigger, the stablizer to the degraded caused by heat or light, reodorant, flowing or slip aids, sterilant and identification tracer agent.
In one aspect of the invention, the surface tension of ink controls by adding the such as commercially available tensio-active agent of one or more surface active materials.The adjustment of ink surface tension makes can be controlled at the moistened surface of various base material such as plastic basis material curing ink.Too high surface tension may cause the mottled appearance in the high area coverage of ink pond and/or printed matter.Too low surface tension may cause ink bleeding too much between different colours ink.Described surface tension is preferably at 20-32mNm -1scope in, more preferably 21-27mNm -1.
Present invention also offers ink group, comprise cyan ink, magenta ink, Yellow ink and black ink (so-called three-color (halftone) block group), at least one of wherein said ink is according to ink of the present invention.All ink in preferred ink group is according to ink of the present invention.Ink in three-color (halftone) block group may be used for by the printing points covered in white substrate combination colour and the tone of producing wide region.
Ink of the present invention optionally can comprise one or more light color ink.Can use the light color form of any colored ink, but preferred color is nattierblue, light magenta and light black.Particularly preferably be pale cyan ink and light magenta ink.Light color ink is used for expanding colour gamut and making printed images high light district level and smooth to the level of shadow area.
Ink group of the present invention can optionally comprise one or more green inks, orange ink and purple ink.These colors expand the colour gamut of the color that can produce further.Preferred purple ink and orange ink, most preferably orange ink.
Ink group of the present invention optionally can comprise white ink.White ink can be used in two ways.When transparent printing on substrates, white ink can be printed on image, can watch image from the negative like this.Alternatively, before printed images, white ink can be used for printing subcoat on colored subtrate.
Even if use the ink of above-mentioned scope, some color is still difficult to produce especially.Wherein, the color printed is necessary with the exact matching of Standard Colors such as company standard look, ink group of the present invention optionally can comprise the ink that one or more have coupling goods color, and it is designed to is not having in chlamydate situation with the printing of pure color form.
Ink of the present invention can produce the image with high gloss facing.This refers to when on the base material that ink is printed on low gloss, there is high ink deposition (such as, image has the place of dark color or dark shade) the image-region ratio image-region with low ink deposition (such as, only having the place of light shade in image) there is obviously higher glossiness.In other words, the high light district of printed matter can have lower glossiness than shadow area.Can be there is place from dark shade to shallow shade (such as, from high gloss to low gloss) that occur in the picture to change from lines clearly, and this may produce pic-eyed printed matter.
In order to provide uniform facing thus improve picture quality, whole printed matter can optionally scribble colorless ink or varnish.But ink of the present invention preferably prints together with colorless ink.Therefore, ink group of the present invention preferably includes colorless ink.
Ejection colorless ink while colored ink of the present invention instead of colorless ink deposit in the blank not having the image of high deposition colored ink or high light district.This means the whole printed matter surface of ink film covering substrates, which results in and have on whole printed matter evenly the printed matter of facing.This printed matter also may often have on whole film evenly ink film weight, this improves the outward appearance of printed matter, because surface image is evenly and transition between colored ink height deposition region to high light district is more level and smooth.
Printhead accounts for a big chunk of entry level printer cost, therefore needs the quantity (quantity of the ink therefore in ink group) keeping printhead few.But the quantity reducing printhead may reduce printing quality and productivity.Therefore, when not endangering printing quality and productivity, need the quantity balancing printhead to make minimizing costs.A preferred ink group of the present invention comprises cyan ink, Yellow ink, magenta ink and black ink.The limited combination of this color can realize having the printed matter of uniform very high gloss, extraordinary gradation and high colour gamut on whole printed matter.The further change of above-mentioned ink group can comprise above-mentioned ink group and add other one or more transparent varnishes, metal ink and white ink.Another example of ink group is cyan ink, Yellow ink, magenta ink and black ink, colorless ink, pale cyan ink, light magenta ink and orange ink.
When ink of the present invention is provided in ink group, in ink group, the surface tension difference of different ink is preferably more than 2mNm -1, more preferably no more than 1mNm -1, be most preferably not exceeding 0.5mNm -1.The surface tension carefully balancing different ink by this way can cause the improvement of print image quality and outward appearance.
Ink group of the present invention optionally can comprise the ink of one or more metal effects.Such as, the use of metal color such as silver color is just becoming and is becoming more and more popular in advertising image.
Conventional solvent-based ink can produce very bright metal effect.Metallic pigment are the form of thin slice or platelet and are randomly-oriented in the liquid ink of drying.When containing solvent ink, because solvent loss in drying process causes ink film thickness to reduce, described thin slice can be arranged in parallel with printed matter surface.Metallic pigment thin slice and the arranged in parallel of printed matter surface cause good reflectivity and metalluster.But the film of generation often has the frictional behaviour of non-constant, this means can easily from printed matter surface removing pigment.Metal ink after UV solidification generally has good frictional behaviour, but often lackluster in appearance, arranges because metallic pigment thin slice is not free in UV solidification process fast.
Metal ink of the present invention overcomes these problems, because described ink is as described below dry in two steps.In solvent evaporation step, sheet metal arranges if having time, makes to produce bright metal effect in final image.But UV curing schedule creates rub resistance film.
Varnish can be used as according to colorless ink of the present invention.In one embodiment of the invention, colorless ink can be used as the varnish of common solvent Base Metal effect ink.Can protect metal effect printed matter with the curable varnish of known UV, but producing higher film weight when spraying these materials makes the metalluster of printed matter dark and gloomy and is harmful to their outward appearance.But the easy volatile solvent that there is relatively large ratio in colorless ink of the present invention makes the film weight of deposition low.Usual UV varnish can produce the film of 12 μm on printed matter surface.By using according to colorless ink of the present invention, film weight can reduce 2-3 μm.Mixing varnish the outward appearance of low film weight to operplate printing product have far away from harmful effect.
Ink of the present invention is mainly designed to print on flexible parent metal, but the character of base material does not limit, and comprises any base material that can carry out ink jet printing, such as glass, metal, plastics and paper.Most preferably flexible parent metal, in particular for the flexible parent metal of graphic printing industry.Example includes but not limited to polyester, eyelet fabric, vinyl substrate, paper etc.Ink of the present invention is particularly suitable for printing on autoadhesion vinyl and banner level PVC base.
Can such as stir with high speed water cooling and stirring device by known method or grind on horizontal bead mill and prepare ink.
printing equipment and method
Use conventional solvent-based ink, the productivity of printer discharges the capability control of a large amount of solvent by system.If put too many wet ink on medium, ink flowing makes the image blurring of printing.For this reason, in ink, preferably the solvent that vapour pressure is high is used.But if solvent vapour pressure is too high, ink drying on print-head nozzle plate may cause spray nozzle clogging.This compromise in solvent selection causes productivity to be restricted.
Due to the productivity that they are lower, the cost of investment of solvent printer must be relatively low to keep commercial benefits.Therefore, keep internal structure simple, there is the least possible printhead to produce the image of reasonable quality.Low-complexity makes these machine easy handling and maintenances.
In recent years, UV curable ink system, in comparatively high productivity scope, wide format figure market, has replaced solvent ink printer to a great extent.Different with solvent printer, the ink heat of deposited on silicon can not obviously be evaporated.On the contrary, material is converted to solid by exposing to the open air under the energy.In most of the cases, the described energy is strong UV light, and it causes the photo-crosslinking of curable molecule to form solid in the presence of photo initiator.
The maximum visible interests of the curable printer of UV are that they realize the ability of high production rate.In most of UV printer, on the printhead sliding support shuttled back and forth, on the one or both sides printing head group, curing light source is installed.In some cases, also curing system is placed between printhead.Typical spacing distance between printhead and solidified cell is less than 100mm, and the translational speed due to printhead sliding support is 1m/s, and the maximum duration between printing and solidification is 0.1s.The UV ink being less than 1 second set time is favourable compared with needing the solvent ink of several minutes time drying.But, must be more complicated than the ink-jet printer for solvent-based ink for the ink-jet printer of UV curable ink, thus more expensive.
Ink of the present invention can use the ink-jet printer being applicable to solventbased inkjet ink to be combined with actinic radiation source to print.
The feature being suitable for the printer of printing solvent based ink jet inks is well known to those skilled in the art, and comprises feature described below.
As mentioned above, the printer being suitable for printing solvent based ink jet inks has lower cost of investment usually, this means that printer often has simple internal structure.In practice, the ink-jet printer that this means to be suitable for printing solvent base oil ink comprises the gravity feed system for ink to be transported to printhead from print cartridge usually.On the contrary, UV printer uses pressurization header tank that ink is transported to printhead, and this makes meniscal position in nozzle controlled.
Because printhead accounts for the significant proportion of whole printer cost, the ink-jet printer being suitable for printing solventbased inkjet ink comprises the printhead of the minimum quantity providing high quality graphic needs.Under any circumstance, because solventbased inkjet ink needs time of more growing dry than UV ink usually, use in a large amount of ink to base material at the many printheads of use and almost there is no advantage, because this causes ink gathering and image blurring.
And the printhead for printing solvent based ink jet inks does not install the device of heating ink, because the viscosity of solvent-based ink is low, therefore do not need in the heating of printhead place to produce sprayable viscosity (compared with UV curable ink).Therefore, known solvent-based ink is at room temperature injected.
Due to the evaporation of solvent, solvent-based ink is easily dry on the nozzle plate.Therefore solvent-based ink printer generally includes and at not used time lid sucker on the print head, can set up solvent evaporation saturated environment, restrain evaporation.Just in case printhead is plugged, described sucker can use peristaltic pump to be used to the ink of sucking-off small volume from blocking, restorability after removing excess of ink with wing.
Ink of the present invention comprises solvent and radiation curable component, therefore and can expose solidification radiation curable component to the open air come dry under actinic irradiation in conjunction with the evaporation of organic solvent.
Ink of the present invention can be used to the printer being suitable for printing common solvent based ink jet inks surprisingly, as long as also provide actinic radiation source.The printhead of the ink-jet printer of usual solvents base oil ink does not have indirect heating.Ink of the present invention can be at room temperature injected, preferably lower than 35 DEG C, or lower than 30 DEG C or about 25 DEG C, therefore with for the printhead of printing solvent based ink jet inks and nozzle adapts.Use the printer for printing common solvent based ink jet inks, the printhead particularly used together with common solvent based ink jet inks, nozzle and ink delivery system, as the basis of printing equipment of the present invention, mean that the cost of printing equipment of the present invention is low.
For before printing ink of the present invention, the printer being suitable for printing common solvent based ink jet inks can be transformed.According to the exact nature of ink and the position of curing light source, the opaque ink feeding component of chemical aspect and this ink compatibility can be used in and/or the Printed Windows on the front of equipment can use UV aperture plate filtering membrane.These are less transformations, can not have significant impact to printing cost or performance.
In one embodiment, printing equipment of the present invention comprises one or more piezoelectricity print on demand head.The ink drop size that preferably described printhead can spray is 50 skins liters or less, more preferably 30 skins liters or less, particularly preferably 10 skins liters or less.
Printing equipment of the present invention comprise once after this ink and substrate contact from this ink the device of evaporating solvent.Be suitable for any device of evaporating solvent from known solventbased inkjet ink can be used in equipment of the present invention.Example well known to a person skilled in the art, comprises moisture eliminator, well heater, air doctor blade and combination thereof.
In one embodiment, by adding heat extraction solvent.To whole base material heating and/or can heat above base material, the irradiation well heater (heating rod, infrared lamp, solid-state I R) that such as use is arranged on the hot-plate (resistance heater, induction heater) under base material or is arranged on above base material.In preferred embodiments, described ink can be injected on the base material of preheating, then moves above the platen of heating.Equipment of the present invention can comprise one or more well heater.
When printing ink of the present invention, preferably before this ink is cured, solvent can be evaporated greatly.Preferably before this ink is cured, all solvents are evaporated substantially.This can be realized by the condition making printing-ink stand usually dry common solvent based ink jet inks.When ink of the present invention, such condition will remove most of solvent, but consider to there is radiation curable component in ink, and the solvent that it is expected to trace will stay in the film.
Solvent evaporation step is considered to important, because it is deemed to define picture quality.Therefore, think that solvent evaporation step result in high gloss printed images, as it is expected to for common solvent base oil ink.And ink is by evaporative loss of solvent greatly, the film causing the printing film formed can obtain than injection equal-volume known radiation curable ink is thinner.This is favourable, because the flexibility that thinner thin film is improved.
In order to obtain best picture quality, and the bleeding controlled between image-region and emergence, preferably by after ink droplet encounters substrate surface, from ink droplet, evaporating solvent is to stop the flowing of ink rapidly, and this step is often referred to as locking (pinning).In order to obtain the image of good quality, preferably this ink is by " heat locking ", namely in order to evaporation of organic solvent, is heated in 5 seconds of encountering, preferably in 1 second, most preferably in 0.5 second.
Different with the solvent-based ink of standard, once solvent is evaporated, this ink can not be considered to complete drying.On the contrary, still staying, surface is full-bodied radiation curable ink.This viscosity is high enough to suppress or obviously hinder ink flow and prevent image from decomposing in the time range needed for this ink of regelate.Once expose to the open air under irradiating source, this ink solidification forms the polymeric membrane of relative thin.The printing film with 1-20 μm of thickness prepared usually by ink of the present invention, preferred 1-10 μm, such as 2-5 μm.Film thickness can use confocal laser scanning microscope, CLSM to measure.
In one embodiment, actinic radiation source is arranged in the downstream of the device from printing-ink evaporating solvent.In other words, place evaporation unit and actinic radiation source, make printing element be exposed to ray before be exposed to the device of evaporating solvent, make evaporating solvent before radiation curable material is cured.
In this embodiment, one or more printhead or irradiating source are placed, and produce ink and are ejected on base material and this printing-ink is exposed to delay between ray, make to be cured front evaporator solvent at this ink.Preferably, the distance between one or more printhead and actinic radiation source is at least 100mm, preferably at least 200mm, more preferably at least 300mm.
Preferably, from printhead, ink is sprayed on base material and this printing-ink cycle be exposed between ray is at least 1 second, preferably at least 5 seconds, more preferably at least 10 seconds.It can be 1-5 minute and longer for being exposed to the typical cycle of ray after injection.
Actinic radiation source can be any actinic radiation source being applicable to solidify radiation curable ink, but is preferably UV light source.Suitable UV light source comprises mercury discharge lamp, fluorescent lamp, photodiode (LEDs), photoflash lamp and combination thereof.One or more mercury discharge lamp, fluorescent lamp or photoflash lamp can be used as irradiating source.When leds are used, these are preferably provided as the multiple LED of a row.
Preferred actinic irradiating source is not ozoniferous light source in use.
In special travelling belt UV solidified cell such as SUVD Svecia UV moisture eliminator, UV irradiating source can be positioned at outside line.But preferred irradiating source is positioned on line, this means that this base material need not remove printing equipment between heating and curing schedule.
Irradiating source can be mobile, this means this irradiating source can be parallel on printing width printhead direction of motion move forward and backward.
In one embodiment, actinic radiation source is positioned on sliding support, makes this actinic radiation source to traverse printing width.This sliding support is placed on the downstream of printer carriage, to provide ink printing on base material and to be exposed to the delay between solidified cell, makes at curing schedule front evaporator solvent.In this embodiment, in order to provide time enough evaporating solvent before curing schedule, actinic radiation source is moved independent of printer carriage, and therefore the motion of printhead is not certainly decelerated.Therefore, total productivity can be improved.
When irradiating source is provided in independently on sliding support, be necessary to provide auxiliary sliding support guardrail, motor and Controlling System.This transformation may cause rolling up of equipment cost.
Preferred irradiating source is static.This means in use, this irradiating source can not move forward and backward on printing width.Contrary actinic radiation source is fixing, and base material moves on print direction relative to this irradiating source.
When actinic radiation source is provided in the printing zone of printer, must avoid the light pollution at printhead place, it may cause solidification too early in nozzle.Prevent the transformation of light pollution, such as lamp adjustable plate, produce extra cost.Therefore preferably irradiating source is positioned at outside the printing zone of printing equipment.Printing zone refers to the transportable region of printhead in printing equipment, thus is also the region that ink is applied to base material.
Preferred printing equipment according to the present invention comprises the static irradiating source be positioned at outside printing zone, is considered to attractive at economic aspect, is therefore suitable for entry level wide format digital mapping and uses.Therefore this embodiment is particularly preferred.Entry level refers to the simplest and the most cheap printer being suitable for wide format digital mapping and using.
By being avoided using the irradiating source of movement by actinic radiation source electricity outside printing zone, the transformation of the costliness potentially to printing equipment can be avoided.And as mentioned above, printing and consolidation zone are separately good to printing ink of the present invention, because this makes at ink by being exposed to before irradiating source solidifies, solvent is evaporated from printing-ink.
Static solidified cell preferably covers whole printing width, is at least 1.6m usually for less wide format drawing printer.
Fluorescent lamp, mercury discharge lamp and photodiode can be used as static solidified cell.
The operation of high pressure mercury discharge lamp may be relatively costly.This lamp unit itself may be heavy with costliness, and often need auxiliary protecting cover to prevent to operator unintentionally UV irradiate.Also the ozone that extracting produces to remove this lamp is needed.And, when high-power lamp relates to high discharging current, need electric ballast, because in use can change for the resistance of the gas of this lamp.Therefore not preferred UV light source according to high pressure mercury discharge lamp of the present invention.
Used LED light source is relatively costly, and comprises that the printing equipment of LED light source that UV irradiates is unlikely is applicable to entry level printer.Therefore, the actinic radiation source comprising used LED is not preferred.But, carry out for the research and development of the UV LED light source of curing inks, it is contemplated that the cost of following LED light source will obviously reduce.In this case, the printing equipment comprising the actinic radiation source comprising LED according to the present invention may be applicable to entry level printing system.
In one embodiment of the invention, irradiating source comprises UV luminescent lamp.
In another embodiment of the invention, irradiating source comprises one or more photoflash lamp.Photoflash lamp decomposes rare gas element by electric discharge between two tungsten electrodes, and such as xenon or Krypton operate.Different with mercury discharge lamp, photoflash lamp does not need at high temperature to operate.Photoflash lamp also has the advantage accessed instantaneously, does not have heat-stable time.Also can adulterate packaged material, prevents the transmission of the wavelength that can produce deleterious ozone.Therefore the operation of photoflash lamp is economical, is therefore applicable to entry level printer.
Photoflash lamp can operate under various modes, comprises cooling pulse pattern and shaping modes.Cooling pulse pattern be when lamp output terminal each close completely before be access in the short period of time very much time, need UV illumination flash lamp.Usually, the intermittent nature of cooling pulse photoflash lamp can make it not be suitable for conventional cure applications, wherein usually needs constant lamp to export.But when photoflash lamp is used at the downstream curing jetted ink of the present invention of printing zone, the intermittent nature of this curing source does not have disadvantageous effect.Such as, for the average production rate normally 0.5m/min of the printer of solventbased inkjet ink, when the ending that printhead sliding support passes through at every turn, base material is 3-6mm by the displacement that printer in fact progressively occurs.This means that base material each time can static 1-3 second, this be greater than lamp under high-power at identical image overlying regions flash of light several times with the time enough of curing inks.As long as the step moved forward at base material starts this lamp simultaneously, the pulse characteristic that lamp exports can provide enough dosage and peak illumination with curing inks, and can not cause the cause thermal damage of base material.
When operating in this mode, photoflash lamp does not launch constant irradiation in use, and therefore a big chunk time of this lamp above base material is " closedown ", it reduces the cause thermal damage risk of temperature sensitive substrates.
The circuit element that generation voltage pulse drives photoflash lamp to need is made up of AC-DC converter, high voltage capacitor and inductor block, is relatively cheap.Make the cost of investment of this lamp and running cost be economical compared to the simplicity of mercury discharge lamp and obviously low average power consumption, be applicable to entry level mixed solvent/UV printer.
But described photoflash lamp preferably operates under shaping modes.Under shaping modes, realize a large amount of instantaneous UV power stage at impulse duration, but owing to not needing to repeat to cause geseous discharge, so extend the life-span of lamp.Regulate and also have superiority, namely interpulse have lower current flowing in described lamp, and infrared (IR) which increase lamp exports.Because interpulse absolute power is low, described lantern festival helps from printing-ink except desolventizing as low power IR well heater.
Photoflash lamp needs cooling during use usually, and the maximum average output power of photoflash lamp depends on the method for cooling of use.For higher output rating, need more complicated method of cooling.If use convected air cooling, maximum average output power is about 0-15W/cm 2if use air blast cooling, maximum average output power is about 15-30W/cm 2if use water cooling, maximum average output power is about 30-60W/cm 2.But, in order to realize ink fast setting, preferably making the output rating of lamp maximize, when providing economic UV irradiating source, needing to balance this demand and the cost that the suitable type of cooling is provided.There is provided water recirculator obviously to increase cost, be therefore unlikely applicable to entry level printer.Therefore, the maximum average output power of described photoflash lamp is preferably about 30W/cm 2, and preferably use the forced air cooling to cool described lamp.
Compared with exporting with IR, the UV that can improve described photoflash lamp by providing high current density exports.This can be realized by the output rating increasing described lamp.The output rating of described lamp is directly proportional to the internal diameter of lamp, and the increase that the UV compared with therefore exporting with I R exports can by using the large diameter lamp with high-power supply to realize.Such as, compared with the 38W/cm being the lamp of 4mm with internal diameter, the lamp that internal diameter is about 10mm can produce 94W/cm.
Use the photoflash lamp that single 1.6m is long, internal diameter is 10mm can need to provide the power supply more than 15kW.Although structure is simple, the power supply of this grade may remain expensive and three-phase supply may be needed to connect.Therefore, preferably irradiating source is formed by a series of shorter lamp along printing width prolongation with the smaller power supply switched between which.Preferred printing element, relatively slowly through printing equipment, therefore before base material moves forward, can make described lamp produce pulse rapidly successively on whole printing width.Owing to being considered to be limited, so the slightly discrepant exposure duration that printed matter experiences on its width is considered to affect picture quality by the step except desolventizing by the picture quality that mixed solvent/radiation curable jetted ink provides.
Fig. 1 shows the skeleton view of the exemplary according to ink-jet printing apparatus of the present invention.This equipment comprises printhead (1), heating unit (2) and UV solidified cell (3).
Fig. 2 shows the sectional view of the exemplary according to ink printing equipment of the present invention.This equipment comprises the printing sliding support of printhead (1), heating unit (2) and comprises the UV solidified cell (3) of reflection shield (4) and bulb (5).
In a particularly preferred embodiment of the present invention, actinic radiation source is low pressure mercury lamp.
Therefore, present invention also offers a kind of method, comprise:
I) by jetted ink ink jet printing of the present invention on base material;
Ii) evaporating solvent from described ink; With
Iii) under the UV of low pressure mercury lamp irradiates, described ink is exposed to the open air.
According in the method for this embodiment, described jetted ink preferably comprises based on gross weight at least 30 % by weight organic solvent of ink, radiation curable oligopolymer, light trigger and optional tinting material.
Preferably, based on the gross weight of ink, in composition, the amount of radiation curable oligopolymer is 2-65%, more preferably 2 % by weight to 45 % by weight, and more preferably 5-35 % by weight, more preferably 8-25 % by weight, most preferably 10 % by weight to 25 % by weight.
The molecular weight of the radiation curable oligopolymer used according to this embodiment is 500g/mol or larger.
As previously mentioned, ink of the present invention can comprise the monomer that one or more molecular weight are 450 or less.Although the monomer of single functionality can be used, preferably use two functionality, three-functionality-degree and higher functional degree monomer in this embodiment.
Based on the gross weight of ink, the ink used according to this preferred embodiment can comprise the radiation curable material that the molecular weight being less than 20 % by weight is less than 450g/mol, or is less than 10 % by weight, is more preferably less than 5 % by weight.In an especially preferred embodiment, described ink is substantially devoid of the radiation curable material that molecular weight is less than 450.
Based on the gross weight of ink, the ink used according to this preferred embodiment can comprise the radiation curable material that the molecular weight that is less than 20 % by weight is less than 600, or is less than 10 % by weight, is more preferably less than 5 % by weight.In an especially preferred embodiment, described ink is substantially devoid of the radiation curable material that molecular weight is less than 600.
According to identical with above to the description of ink of the present invention of other preferred characteristics of the operable ink of this preferred embodiment.
Medium pressure mercury lamp widely uses the UV solidification of the ink being embodied as certain limit Application Design in printing industry.Medium pressure mercury lamp is relatively inefficent, usually only has the energy input of 15% to be converted to required UV and irradiates; Remaining input energy transformation is infrared radiation/heat and visible ray.The high calorie of medium pressure mercury lamp exports and may cause for the degraded of heat-sensitive substrate material in some printing application or the problem of distortion.A solution uses color separation reflection shield, and UV away from base material, only irradiates and focuses on material by it by heat guiding.But these limit effect of described lamp and substantially increase cost.
Low pressure mercury lamp is more effective than medium pressure mercury lamp.The energy input of about 35% is converted to UV and irradiates, and the wavelength of 85% is 254nm (UVC).Therefore, the heat that in using, these lamps produce is fewer than medium pressure mercury lamp, this means that they run more economical and unlikely damage sensitive material.And low pressure mercury lamp can manufacture in use not ozoniferous mode, therefore uses safer than medium pressure mercury lamp.
Although low pressure mercury lamp is widely used in Water warfare industry, also do not find the widespread use in printing industry.The output area of usual medium pressure mercury lamp is 80-240W/cm.On the contrary, the maximum output of low pressure mercury lamp is about 30-440mW/cm, this means that the peak illumination of low pressure mercury lamp is also low.The low output rating of these lamps and low peak illumination show that they can not provide the solidification of effective radiation curable jetted ink.
Find surprisingly to use low pressure mercury lamp to solidify according to jetted ink of the present invention, particularly comprised the jetted ink of the present invention of radiation curable oligopolymer.
In this preferred embodiment of the present invention, solidify this ink by being exposed to the open air under the UV of low pressure mercury lamp irradiates by ink.Single low pressure mercury lamp or two or more low pressure mercury lamp can be used.
IUPAC technical term of chemistry compilation (PAC, 2007,79,293 " glossaries of the term used in photochemistry ", the third edition (IUPAC recommends 2006), doi:10.1351/pac200779030293) low pressure mercury lamp is described for " to comprise about 0.1Pa (0.75 × 10 -3torr; 1Torr=133.3Pa) pressure under the resonance lamp of mercury vapour ".At 25 DEG C, such lamp mainly 253.7 and 184.9nm place luminous.They are also referred to as germicidal lamp.There are cold cathode and hot-cathode and cool electrodeless (microwave-excitation) low pressure mercury lamp.Wood lamp is a kind of low pressure mercury arc with the fluorescent layer of increase, and it is luminous at UV-A spectral region (315-400nm).
Low pressure mercury lamp widely uses in Water warfare industry, therefore can extensively obtain.
As mentioned above, low pressure mercury lamp mainly sends the UV irradiation that peak wavelength is about 254nm, but can by changing with the internal surface of fluorescent powder coating lamp the wavelength irradiated.In a preferred embodiment of described lamp, there is no such fluorescent coating.In the method for the invention, described lamp preferably sends the irradiation that peak wavelength is about 254nm, or in other words, natural or that wavelength is constant irradiation is sent by the mercury vapour in low-voltage lamp environment.
The use of fluorescent coating can cause the reduction of lamp efficiency.But unstressed configuration powder lamp preferably used according to the invention produces the efficiency of UVC more than 45%.This high-level efficiency contributes to making the running cost of solidified cell to minimize.
In low pressure mercury lamp, UV exports and varies with temperature.When first connecting described lamp, liquid mercury starts evaporation, and along with the rising of temperature, the vapour pressure of mercury reaches optimum level, and UVC irradiates output and reaches maximum.Along with the temperature of described lamp raises further, vapour pressure continues to raise, and decreases UVC and exports.Therefore, under the optimum temps that can reach maximum UVC output, operate low pressure mercury lamp, for the low-voltage lamp of standard, this temperature is about 25-40 DEG C usually.But the energy input of this restrict in service temperature, because if energy input is too high, the temperature of described lamp may be elevated to more than optimum temps.Restriction energy input just limits accessible maximum UV and exports.Therefore, the accessible maximum UV of low pressure mercury lamp exports and is limited by service temperature and energy input.The linear power densities of low pressure mercury lamp in their normal set-up of standard is less than 380mW/cm.Such as, but effective overall power density of U-shaped lamp can reach its twice, 650mW/cm.
Be enough to solidify ink of the present invention in acceptable time range although the UVC of the low pressure mercury lamp of standard exports, UVC curing dose is preferably carried in the short period of time, makes curing speed faster.
In a preferred embodiment of the invention, low pressure mercury lamp is amalgam vapour lamp.In amalgam vapour lamp, usually use the amalgam of mercury, usually with bismuth and/or indium, replacement liquid mercury.But, other suitable material that mutually perhaps can form amalgam with mercury with mercury can be used to replace bismuth or indium.Amalgam vapour lamp has the spectrum identical with conventional low pressure mercury lamp and exports, as shown in Figure 3.In operation, along with temperature raises, amalgam discharges mercury vapour gradually, but if pressure is too high, steam is reuptaked.This inherent regulation refers at a higher temperature, about 80-160 DEG C, such as 83 DEG C, according to type and the manufacturers of lamp, realizes best mercury vapour pressure.Therefore amalgam vapour lamp runs under the optimum temps higher than standard low pressure mercury lamp, this means to allow higher energy input.Higher energy input causes adjoint UVC to export to be increased, and this prolongation run duration at lamp keeps stable.
Usually, amalgam vapour lamp can up at the temperature of 140 DEG C, run under more than the linear power densities of 380mW/cm, and this lamp can realize approximating the output that conventional low pressure mercury lamp exports five times.Time compared with the low pressure mercury lamp of routine, the ink aspect that is dry and solidification the present invention use that is combined in of the heat that the irradiation of increase and amalgam vapour lamp produce provides useful advantage.
In a preferred embodiment of the invention, the linear power densities of cure lamp at below 2000mW/cm, preferred 200mW/cm to 1500mW/cm, more preferably 380mW/cm to 1,500mW/cm.In a preferred embodiment, described linear power densities is 380mW/cm to 1,200mW/cm, in a most preferred embodiment, is 380-1000mW/cm or 500-1000mW/cm.
The current density of standard low pressure mercury lamp is no more than 0.45Amps/cm, and the current density of amalgam vapour lamp is more than this level.
The temperature of amalgam vapour lamp can be controlled to keep best UV light output.Temperature controls to realize by being soaked in water by lamp in quartz sleeve.Except the electrical insulating property provided relative to water, lamp ambient air gap prevents by water excessively cold.By controlling the water yield flowing through lamp, the optimum temps that the maximum UV of lamp exports can be kept.Although convenient, the method is not preferred, because it needs the additional cost bearing cooling agent.
In a preferred embodiment, air is blown over low pressure mercury lamp to control the temperature of lamp.In another preferred embodiment, the top of printed images is directed into help before curing except desolventizing by the forced air that lamp heats.Such as, that can cover in lamp transmitting place one or more blower fan below, with extracting and the excessive heat air carrying printing process middle and upper reaches, and help drying and locking printed images, thus the efficiency of raising printer.
Described low pressure mercury lamp preferably uses to regulate the electric current by lamp together with auxiliary ballast electronics.Eurypalynous barretter perhaps can be used.Preferably use electric ballast input dominant frequency being converted to the frequency being greater than lamp ionized plasma time of relaxation in the present invention, thus keep best light output.
In a preferred embodiment, provide with electric ballast that the is quick or operation of OnNow pattern, wherein the electrode of low pressure mercury lamp can be preheated to reduce the electrode damage caused by frequent transitions before triggering.Although implement more expensive than cold start-up method, preferably preheating, because the preferred amalgam vapour lamp of the present invention is powerful, at high temperature operates and probably frequent transitions in using.
Low pressure mercury lamp is luminous along all directions.Therefore, in order to UV cured printed image effectively, the wide part of UV that described lamp is preferably combined with at least one reflection shield to ensure to launch is directed into print surface effectively.Described reflection shield is preferably made up of the material effectively reflecting UV light with minimal losses, and such as aluminium, it has the reflection efficiency being greater than 80%.Fuzzy in order to what prevent the mirror surface in long-term UV exposure from modifying, preferred pre-galvanized aluminium, such as can purchased from the 320G of Alanod.This material by rolling or bending can easily forming curves or chamfer shape to provide effective reflection shield.
In one embodiment, described reflection shield is preferably oval, therefore guides the irradiation on printing element to focus on a fine rule, thus improves the peak illumination on printing element." oval reflection shield " is term known in the art, refers to the reflection shield of the general shape had as shown in Figure 4.
The finite diameter of low pressure mercury lamp prevents all utilizing emitted lights to be produced by the center of ellipse.Therefore, in a preferred embodiment, diameter is less than 30mm, is preferably less than 20mm, and the low pressure mercury lamp and the oval reflection shield that are more preferably less than 10mm combinationally use, to improve the peak illumination on base material further.
In one embodiment, the bulb part of low pressure mercury lamp scribbles reflectance coating, and the irradiation produced by bulb is like this drawn towards print surface.Fig. 4 is the sectional view of the low pressure mercury lamp with reflectance coating.Lamp (1) comprises the bulb (3) producing UV and irradiate.It is inner that this bulb is assemblied in reflection shield (5).Tube face away from print surface (7) direction scribbles reflectance coating (9), and it will irradiate (10) and guides print surface (7) into by bulb, therefore improve the efficiency of lamp.And the existence of reflectance coating provides gap (11) in reflection shield (5), makes lamp cool.Reflecting material can be any material that reflection UVC irradiates, and plated film can by such as smearing or vacuum moulding machine applying.
Be printed on total UV dosage that ink on base material receives and this base material to move and be inversely proportional to by the speed of lamp.Although compared with medium pressure mercury lamp, have relatively low power output according to the low pressure mercury lamp that the preferred embodiment of the invention uses, the time that the use of static lamp makes printing-ink expose to the open air under light irradiation is longer than the large form printer of traditional sweep type.Therefore, the total dose that this low-voltage lamp provides can exceed the sweep type solidified cell of the higher output lamp of use.
The shell of low pressure mercury lamp is made up of the quartz melting usually, and this makes it possible to the lamp of production length more than one meter.In order to ensure using, solidified cell on static line is uniform curing on whole printing width, and the lamp preferably providing arc length to exceed printing width some centimetres is to offset the emission differences of ate electrode.Add electrode package, the length of final lamp can close to 3m sometimes.For the shell of wide diameter, such lamp length can be reached.But thinner lantern festival is more crisp, need there is additional support over their length, this may hinder the profile of irradiation.In this case, the arrangement of some slot types or staggered less lamp is preferably used to realize whole width solidification.
The invention provides a kind of inkjet printing methods using printing equipment as above and ink.
Invention further provides a kind of jetted ink print cartridge of the jetted ink containing, for example the present invention's definition.Described print cartridge comprises an ink reservoir and is suitable for one the ink delivery port that is connected with ink-jet printer.
To describe the present invention with the following Examples now, embodiment is not be intended to limit the present invention.
Embodiment
I) colored ink
Black, cyan, magenta and yellow radically curing ink jet ink formulations (embodiment 1-12), magenta Cationic curing ink jet inks ink (embodiment 13) and the cyan contrasted, magenta, yellow and black ink-jet inks formula (comparative example 1-4) have the composition of table shown in 1-4, make by mixing described component with the amount provided.The consumption provided is the weight percentage based on total weight.
UVE2500-TP20 is a kind of epoxy group(ing) phenolic varnish origoester acrylate purchased from Polymer Technologies, Nippon Gohsei 7630B be a kind of at 60 DEG C viscosity be the six functionality urethane acrylates of 6.9Pa.s, Tegoglide 410 is a kind of polyether siloxane copolymer sheets purchased from Evonik, Epikote 1001 is a kind of bis-phenol A diepoxide oligopolymer, OXT221 is difunctionality oxetane monomer, and Elvacite 2013 is a kind of acrylic copolymer resin.
Optical density(OD) uses the SpectroEye spectrophotometer measurement of GretagMacbeth.
Table 1
Table 2
Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
Black Cyan Magenta Yellow
Diethylene glycol diethyl ether 32.5 33.2 32.8 32.4
Propylene glycol propyl ether 20.0 20.0 20.0 20.0
Gamma-butyrolactone 16.5 16.3 15.5 16.4
Nippon Gohsei 763 0B 18.5 18.0 14.0 11.3
Irgacure 819 4.0 4.0 4.0 4.0
Irgacure 2959 2.0 2.0 2.0 2.0
Green pigment dispersion liquid 6.0
Yellow Pigment Dispersion 13.4
Magenta pigment dispersion liquid 11.2
Black pigment dispersion liquid 6.0
UV12 stablizer 0.5 0.5 0.5 0.5
Table 3
Embodiment 13
Shallow magenta
Diethylene glycol diethyl ether 36.97
Propylene carbonate 23.73
Epikote 1001 7.46
OXT221 21.84
Esacure 1064 8.0
Magenta pigment dispersion liquid 2.0
Table 4
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Cyan Magenta Yellow Black
Diethylene glycol diethyl ether 52.99 48.84 51.4 50.4
Propylene carbonate 35.35 32.56 33.4 33.57
Elvacite2013 6.74 5.35 5.51 6.00
Tegoglide 410 0.03 0.03 0.03 0.03
Green pigment dispersion liquid 4.89 - - -
Magenta pigment dispersion liquid - 13.22 - -
Yellow Pigment Dispersion - - 9.66 -
Black pigment dispersion liquid - - - 10.0
With the 2K rod of deposition 12 microns of wet film weight by embodiment 1-8,13 and the ink of comparative example 1 be sampled on autoadhesion vinyl substrate (Profiscreen, Igepa).Dry ink film three minutes at 60 DEG C in an oven.The continuous oven run under 20 ms/min that two 80W/cm medium pressure mercury lamps are housed is used to be exposed to the open air under uv illumination by the dry film of embodiment 1-8 and 13.
By assessing the relative solvent resistance of the rear printed matter of solidification with the fabric friction be immersed in Virahol.Two frictions number (maximum 100) that base material needs are penetrated under recording often kind of situation.Result display in table 5.
Table 5
Embodiment Penetrate two IPA friction numbers of film
1 85
2 100
3 70
4 100+
5 100+
6 100+
7 50
8 50
13 40
Comparative example 1 3
Maxjet 220 printer that the ink of embodiment 1-4 and comparative example 1-4 uses Mutoh to provide is printed on autoadhesion vinyl substrate (IMAGin JT5929P, MACtac).Primary colors is obtained by the ink printing embodiment 1-4 and comparative example 1-4 on single layer.Combination colour by covering the second color to obtain (see table 6) in the first color.Printing and the details of drying show below:
Pattern:
Printing mode: 540 × 720DPI 4-Pass Var.
Head: 1234
Site size: conventional (SML)
Highly: medium
Pattern: mark/quality
Sweep length: data
Print additional: 1
Vacuum: conventional
Bidi: selection
Distance: 0
Thickness: 210
Interval: 0
Screen: Speed Screen
Following well heater setting is used to all printing samples:
Preheater, A 50℃
Fixer, B 40℃
Rearmounted fixer, C 50℃
Moisture eliminator, D 50℃
After oven dry, the ink of embodiment 1-4 uses the continuous solidified cell of Svecia being furnished with a 80W/cm medium pressure mercury lamp to expose to the open air under ultraviolet light.Described sample is cured under the tape speed of 10m/ minute.
Assessment ink resistance to isopropyl alcoholic as above.
Glossiness uses 20,/60,/85 3 glossometers purchased from Sheen instrument to measure.Glossiness is determined from 20 degree and 60 degree of angular measurements.
Result is shown in Table 6.
As can be seen from the above results, the ink of embodiment, compared with the composition based on prior art, provides the solvent resistance of improvement and the glossiness of Geng Gao.
Ii) colorless finish
By mixing the component of specified rate, prepare the colourless ink jet ink formulations (embodiment 14) with component shown in table 7.The consumption provided is the weight percentage based on total weight.
Etermer 6146 is six functionality aliphatic urethane acrylate oligopolymer purchased from Eternal resin.
Table 7
Embodiment 14
Diethylene glycol ether 44.4
Propylene carbonate 25.6
Etermer 6146 27.0
Irgacure 819 2.0
Irgacure 2959 1.0
Viscosity 6.07mPa.s
Use Mutoh Valuejet VJ 1304E printer by solvent-based argentine ink (purchased from the Jetfluid of Eckart silver) to be printed on Mactac JT5929P autoadhesion vinyl substrate and to make its dry.The colorless ink of embodiment 14 rod of 12 microns No. 2K is sampled on the metal ink of printing.Use the medium pressure mercury lamp of two 80W/cm under the tape speed of per minute 20 meters before UV solidification, film was 60 DEG C of dryings 3 minutes.
The resistance to isopropyl alcoholic of the assessment operplate printing product of japanning and the operplate printing product of non-japanning.Soft fabric is immersed in Virahol, in each case two friction numbers of record removing metallic film needs.Assess resistance to metal to-metal contact or the complexity from surface from metal pigment by this printed matter of fabric abrasive (1 pair of friction) by softness, and observe silver color and transfer on fabric.Result is shown in following table 8.
Table 8
Two IPA friction numbers of removing operplate printing Resistance to metal to-metal contact
Non-japanning printed matter 1 Silver color is obviously transferred on fabric
The printed matter of japanning 25 Silver color is not transferred on fabric
Find that the application of varnish significantly improves the solvent resistance of metal ink and resistance to metal to-metal contact.And the metalluster of varnish on printed matter only has minimum impact.
Iii) low pressure mercury lamp
By mixing the component of specified rate, prepared have component shown in table 9 and 10 according to cyan ink-jet ink formula of the present invention (embodiment 15 and 16) and contrast cyan ink-jet ink formula (comparative example 5).
The novolak origoester acrylate of UVE2500 to be molecular weight be 640g/mol, the aromatics six functionality urethane acrylate of Etercure 6146-100 to be a kind of molecular weight be 770g/mol, the molecular weight of hexanediol diacrylate is 226g/mol, the molecular weight of dipropylene glycol diacrylate to be 252g/mol, Sartomer CN964A85 be 85% the blend of molecular weight to be the urethane acrylate oligomer of 3700g/mol and molecular weight the be diacrylate tripropylene glycol ester of 300g/mol.
Table 9
Embodiment 15 Embodiment 16
UVE2500 (100% solid) 16.17 -
Etercure 6146-100 - 21.00
Propylene carbonate 26.59 25.0
Diethylene glycol ether 45.24 42.00
Irgacure 819 4.0 4.0
I rgacure 2959 2.0 2.0
Green pigment dispersion liquid * 6.0 6.0
Table 10
The 2K rod of deposition 12 microns of wet films is used to be sampled on autoadhesion vinyl substrate (Mactac Imagin JT5929P) by the ink of embodiment 15 and 16 and comparative example 5.The ink print of embodiment 15 and 16 is dried 3 minutes at 60 DEG C.Then, this ink exposes 1 minute to the open air at low pressure mercury lamp (being provided by the UV Systems company) 1cm of distance 254nm wavelength.
This ink carries out state of cure as described below and the test of solvent resistance.Be exposed to before and after low pressure mercury lamp at ink film and carry out this test, result is shown in Table 11.
state of cure is tested
Assess the state of cure of ink film and give classification as follows.
5=film complete drying and can not being removed by finger nail cut
4=film is dry, but soft surface and easily marking
3=film is dry, but can be crossed out by finger nail
2=membrane portions is solidified, but can darken from base material
After 1=exposes, film properties does not change, wet film
resistance to IPA test
The fabric friction ink film soaked with Virahol.Write down two friction number of removing priming color and two friction numbers of film damage.
Table 11
Can see from table 11, after exposing to the open air under low pressure mercury lamp, the ink of embodiment 15 and 16 all solidifies very well, gives the resistance to isopropyl alcoholic that desciccator diaphragm is good.But, do not show any obvious change at ink film aspect of performance after the ink of comparative example 5 exposes to the open air under low pressure mercury lamp, show that ink does not solidify.
Although do not wish to be bound by theory, believing that the existence of radiation curable oligopolymer in jetted ink decreases must be polymerized to produce the number of the unsaturated link(age) of solid ink film.This means that this ink can solidify with the UV of relative low dose, this can realize with low pressure mercury lamp.
In order to further research, prepared comparative example 6-8, the monomer component wherein in comparative example 5 is replaced by Sartomer CN964A85 part.Component and the viscosity of the ink of comparative example 5-8 are shown in Table 12.
Table 12
Component Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8
Hexanediol diacrylate 38.7 28.6 18.55 8.55
Dipropylene glycol diacrylate 38.7 28.6 18.55 8.55
Firstcure ST1 0.8 0.8 0.8 0.8
Sartomer CN964 A85 9.7 29.9 50.0 70.0
Irgacure 819 4.0 4.0 4.0 4.0
Irgacure 2959 2.0 2.0 2.0 2.0
Byk 307 0.1 0.1 0.1 0.1
Green pigment dispersion liquid * 6.0 6.0 6.0 6.0
The viscosity of 25 DEG C 17.6mPa.s 77.0mPa.s 500mPa.s 2500mPa.s
The ink of comparative example 5-8 is sampled on vinyl substrate, and as embodiment 15 and 16 describe solidification.As mentioned above, test the state of cure of this ink and resistance to IPA, result is shown in Table 13.
Table 13
Result confirms that the per-cent of lower molecular weight curable materials in component reduces, and cure response when exposing to the open air under low pressure mercury lamp improves.But comparative example 7 and 8, due to they very high viscosity, is not suitable for use in jetted ink completely.The ink of embodiment 5 and 6 has the viscosity of 6.23mPa.s and 5.94mPa.s respectively at 25 DEG C, be therefore suitable for spray ink Printing.
Prepare the composition A with formula shown in table 14.The ink of composition A is identical with the ink of embodiment 15, but UVE2500 oligopolymer is replaced by the three vinylformic acid trishydroxymethyl propyl ester (SR351) that molecular weight is 296g/mol.Then the blend of embodiment 15 as shown in Table 15 and the various ratio of composition A is prepared.As embodiment 15 describes above, this blended ink is printed and exposes to the open air under the UV of low pressure mercury lamp irradiates.The state of cure of this printing film of test described above and resistance to IPA, result is shown in Table 15.
Table 14
Composition A
SR351(TMPTA)Sartomer 16.17
NSC 11801 26.59
Diethylene glycol ether 45.24
Irgacure 819 4.0
Irgacure 2959 2.0
Green pigment dispersion liquid * 6.0
Table 15
As can be seen from above-mentioned data, the existence of low molecular weight propylene acid ester monomer reduces the ability to cure that ink exposes to the open air under low pressure mercury lamp, thus reduces the solvent resistance of film.
Prepare the composition K with formula shown in table 16.Composition K is the base composition not comprising light trigger.Then composition K is used to the ink with formula shown in table 9 manufacturing embodiment of the present invention 17-27.
As embodiment 15 and 16 describes above, the ink of embodiment 17-27 is printed, dries and solidifies.The resistance to IPA of this printing film of assessment described above, result is shown in Table 17.
Table 16
Composition K
Diethylene glycol ether 44.4
Propylene carbonate 26.45
UVE 2500-80 17.15
Green pigment dispersion liquid * 6.0
Amount to 94.0
Table 17
17 18 19 20 21 22 23 24 25 26 27
Composition K 94.0 94.0 96.0 96.0 95.0 95.0 95.0 90.0 90.0 90.0 90.0
Irgacure 2959 2.0 2.0 2.0 2.0 - 5.0 - - - - -
Luderin TP0 4.0 - - - - - - - - - -
Irgacure 819 - 4.0 - - - - - - - - -
Igacure 907 - - 2.0 - - - - - - -
Irgacure 369 - - - 2.0 - - - - - - -
Iracure 651 - - - - 5.0 - - - - - -
Igacure 184 - - - - - - 5 - - - -
Genocure EPD - - - - - - 5 5 5 5
Isopropyl thioxanthone - - - - - - - 5 - - -
1-chloro-4-isopropoxy thioxanthone - - - - - - - - 5 - -
Benzophenone - - - - - - - - - 5 -
Phenyl benzophenone - - - - - - - - - - 5
Resistance to IPA (two friction) 30 30 27 38 20 22 23 19 23 36 33
As can be seen from Table 17, many combinations of standard light initiator are suitable for being combined with low pressure mercury lamp according to the present invention.
Prepare the ink of the embodiment 28 with component shown in table 18.
Table 18
As embodiment 15 and 16 describes, the ink of embodiment 28 is printed and dries.
Obtained ink film exposes to the open air under standard low pressure mercury lamp (the Triplebright 254nm purchased from UV Systems company) or amalgam low pressure mercury lamp (Heraeus NNI50/26XL) as above-mentioned.Two kinds of lamps all operate under maximum output.In each case, measure generation and have the exposure duration of resistance to IPA needed for the films of 40 pairs of frictions, result is shown in Table 19.
Table 19
As can be seen from above-mentioned solidification test, amalgam vapour lamp provides the exposure duration obviously reduced to reach the target of cured film 40 pairs of IPA frictions.
Repeat above-mentioned test, but be switched on 20 minutes and film is exposed to the open air 60 seconds exposing headlight to the open air in this case.Test described above exposes the solvent resistance of rear film to the open air, and result is shown in Table 20.
Table 20
Lamp IPA solvent pairs rubs
Heraeus NNI50/26XL 80
Triplebright 254nm 30
* green pigment dispersion composition
Component Percentage ratio
Disperbyk 168 20.0
Rapicure DVE3 50.0
Irgalite blue GLVO 30.0

Claims (73)

1. a jetted ink, comprises based on the organic solvent of total weight at least 30 % by weight, radiation curable material, light trigger and optional tinting material.
2. jetted ink according to claim 1, wherein based on the gross weight of ink, the amount of organic solvent is at least 50 % by weight.
3. jetted ink according to claim 1 and 2, wherein based on the gross weight of ink, the amount of organic solvent is at least 55 % by weight.
4. jetted ink according to claim 1 and 2, wherein based on the gross weight of ink, the amount of organic solvent is 50 % by weight to 80 % by weight, preferably 60 % by weight to 75 % by weight.
5. the jetted ink according to aforementioned any one claim, wherein said solvent is selected from glycol ethers, organic carbonate, lactone and their mixture.
6. jetted ink according to claim 5, wherein said solvent is selected from the mixture of propylene carbonate and propylene carbonate and one or more glycol ethers.
7. jetted ink according to claim 5, wherein said solvent is selected from gamma-butyrolactone and the mixture of one or more glycol ethers and the mixture of gamma-butyrolactone, one or more glycol ethers and propylene carbonate.
8. the jetted ink according to aforementioned any one claim, based on the gross weight of ink, comprises the water being less than 5 % by weight.
9. the jetted ink according to aforementioned any one claim, wherein based on the gross weight of ink, the amount of radiation curable material is 2 % by weight to 65 % by weight, be preferably 2 % by weight to 45 % by weight, be more preferably 5-35 % by weight, be more preferably 8-25 % by weight, most preferably be 10 % by weight to 25 % by weight.
10. the jetted ink according to aforementioned any one claim, wherein said radiation curable material comprises radiation curable oligopolymer.
11. jetted inks according to claim 10, wherein said radiation curable oligopolymer comprises polyester backbone, polyurethane backbone, epoxy main chains or polyether backbone.
12. jetted inks according to claim 10 or 11, the molecular weight of wherein said radiation curable oligopolymer is 500-4000, more preferably 600-4000.
13. jetted inks according to aforementioned any one claim, wherein said radiation curable material can be polymerized by Raolical polymerizable.
14. jetted inks according to claim 13, wherein based on the gross weight of the radiation curable material existed in ink, described radiation curable material comprises the free radical curable oligomers of 50-100 % by weight, preferably 75-100 % by weight and the free radical curable monomer of 0-50 % by weight, preferably 0-25 % by weight.
15. jetted inks according to aforementioned any one claim, wherein said radiation curable material comprises and has (methyl) acrylate-based oligopolymer or two or more has the mixture of (methyl) acrylate-based oligopolymer.
16. jetted inks according to claim 15, wherein said radiation curable material comprises urethane acrylate oligomer.
17. jetted inks according to aforementioned any one claim, wherein said light trigger is free radical photo-initiation.
18. jetted inks according to aforementioned any one claim, based on total weight, it comprises (methyl) acrylate that the molecular weight that is less than 20 % by weight is less than 450, is preferably less than 10 % by weight, is more preferably less than 5 % by weight.
19. jetted inks according to aforementioned any one claim, based on total weight, it comprises (methyl) acrylate that the molecular weight that is less than 20 % by weight is less than 600, is preferably less than 10 % by weight, is more preferably less than 5 % by weight.
20. jetted inks according to aforementioned any one claim, it is substantially free of (methyl) acrylate that molecular weight is less than 450.
21. jetted inks according to aforementioned any one claim, comprise the organic solvent of the gross weight at least 50 % by weight based on ink; Wherein based on the gross weight of the radiation curable material existed in ink, the molecular weight that described radiation curable material comprises 50-100 % by weight to be the free radical curable oligomers of 600-4000 and the molecular weight of 0-50 % by weight be 450 or less free radical curable monomer; Wherein said light trigger is free radical photo-initiation.
22. jetted inks according to any one of claim 1-12, wherein said radiation curable material can be polymerized by cationic polymerization.
23. jetted inks according to claim 22, wherein said radiation curable material is selected from trimethylene oxide, cycloaliphatic epoxides, bisphenol A epoxide, epoxy novolac and their mixture.
24. jetted inks according to aforementioned any one claim, wherein said radiation curable material comprises the composition of the material of free redical polymerization and cationically polymerizable.
25. 1 kinds of ink groups, comprise cyan ink, magenta ink, Yellow ink and black ink, and at least one of wherein said ink is the ink as defined in any one of claim 1-24.
26. 1 kinds of Inkjet Cartridges, comprise the ink as defined in any one of claim 1-24.
27. 1 kinds of base materials, have the ink as defined in any one of claim 1-24 be printed thereon.
28. if the ink that defines in any one of claim 1-24 is as the purposes of varnish, and wherein said ink is colorless ink.
29. 1 kinds of ink-jet printing apparatus for printing solvent based ink jet inks, comprise at least one printhead, for the device of evaporating solvent from printing-ink and actinic radiation source.
30. ink-jet printing apparatus according to claim 29, comprise the jetted ink source as defined in any one of claim 1-24 in addition.
31. ink-jet printing apparatus according to claim 29 or 30, wherein at least one printhead is piezoelectricity print on demand head.
32. ink-jet printing apparatus according to any one of claim 29-31, wherein at least one printhead can rise following drop size ink-jet with 50 skins, below preferably 30 skins rise, below particularly preferably 10 skins rise.
33. ink-jet printing apparatus according to any one of claim 29-32, wherein said actinic radiation source is arranged in the downstream for the device from printing-ink evaporating solvent.
34. ink-jet printing apparatus according to any one of claim 29-33, the distance wherein between at least one printhead and actinic radiation source is at least 100mm, preferably at least 200mm, more preferably at least 300mm.
35. ink-jet printing apparatus according to any one of claim 29-34, wherein said actinic radiation source is UV light source.
36. ink-jet printing apparatus according to claim 35, wherein said UV light source comprises mercury discharge lamp, LED, photoflash lamp, UV luminescent lamp and combination thereof.
37. ink-jet printing apparatus according to claim 35 or 36, wherein said UV light source does not produce ozone in use.
38. ink-jet printing apparatus according to any one of claim 29-37, wherein said actinic radiation source is positioned at outside the printing zone of printing equipment.
39. ink-jet printing apparatus according to any one of claim 29-38, wherein said actinic radiation source is static in use.
40. ink-jet printing apparatus according to any one of claim 29-39, wherein said actinic radiation source comprises one or more photoflash lamp or one or more luminescent lamp or their combination.
41. ink-jet printing apparatus according to claim 40, each maximum average power of wherein said one or more photoflash lamp exports and is about 30W/cm.
42. ink-jet printing apparatus according to any one of claim 40-42, comprise the forced air cooling in addition.
43. ink-jet printing apparatus according to any one of claim 40-43, wherein said actinic radiation source to be included on one or more row or on staggered col along a series of lamps that printing width extends.
44. ink-jet printing apparatus according to any one of claim 29-39, wherein said actinic radiation source is low pressure mercury lamp.
45. ink-jet printing apparatus according to claim 45, wherein said low pressure mercury lamp is amalgam vapour lamp.
46. ink-jet printing apparatus according to claim 45, the linear power densities of wherein said lamp is 200-1,500mW/cm.
47. ink-jet printing apparatus according to claim 45 or 46, the power supply of wherein said lamp comprises fast or OnNow pattern.
48. ink-jet printing apparatus according to any one of claim 44-47, wherein said lamp is combined with at least one reflection shield.
49. ink-jet printing apparatus according to any one of claim 44-48, wherein said reflection shield is oval reflection shield.
50. ink-jet printing apparatus according to claim 49, the diameter of wherein said lamp is less than 30mm, is preferably less than 20mm, is more preferably less than 11mm, further preferred 10mm or following.
51. purposes of equipment in ink jet printing method as defined in any one of claim 29-50.
52. 1 kinds of methods, comprise:
I) by the ink jet printable that defines in such as any one of claim 1-24 on base material;
Ii) from printing-ink, solvent is at least partially evaporated; With
Iii) printing-ink is exposed to the open air under actinic radiation solidify radiation curable material.
53. methods according to claim 52, wherein said ink is being less than at 35 DEG C injected, is preferably less than 30 DEG C.
54. methods according to claim 52 or 53, wherein the ink jet-print head of ink jet is not heated.
55. methods according to any one of claim 52-54, wherein said ink rise with 50 skins or less drop size injected, preferably 30 skins rise or less, and particularly preferably 10 skins rise or less.
56. methods according to any one of claim 52-55, wherein before described ink is cured, evaporation section solvent from printing-ink.
57. methods according to any one of claim 52-56, wherein before described ink is cured, evaporate all solvents substantially from printing-ink.
58. methods according to any one of claim 52-57, wherein carry out evaporating solvent by heating printing-ink.
59. methods according to claim 58, wherein said ink is heated the time of 1 second to 25 minutes.
60. methods according to claim 58 or 59, wherein in order to evaporation of organic solvent, printing-ink is directed onto at ink in 5 seconds on base material and is heated, preferably in 1 second, most preferably in 0.5 second.
61. methods according to any one of claim 52-60, to be wherein sprayed on ink base material and by this printing-ink from printhead that the cycle be exposed between actinic rays is at least 1 second, preferably at least 5 seconds, more preferably at least 10 seconds.
62. methods according to any one of claim 52-61, wherein said base material is flexible parent metal.
63. methods according to claim 68, wherein said flexible parent metal is selected from plastics or processes or untreated paper.
64. methods according to claim 63, wherein said flexible parent metal is (self adhesion) vinyl or banner level PVC base.
65. methods according to any one of claim 52-64, use the equipment as defined in any one of claim 29-50.
66. methods according to any one of claim 52-64, wherein step I ii) UV that is included in low pressure mercury lamp exposes described ink to the open air under irradiating.
67. methods according to claim 66, wherein said ink comprises based on the organic solvent of total weight at least 30 % by weight, radiation curable material, light trigger and optional tinting material.
68. methods according to claim 66 or 67, wherein based on the gross weight of ink, the amount of radiation curable oligopolymer is 2-65 % by weight, be preferably 2 % by weight to 45 % by weight, be more preferably 5-35 % by weight, be more preferably 8-25 % by weight, most preferably be 10 % by weight to 25 % by weight.
69. methods according to any one of claim 66-68, wherein said ink is substantially free of the radiation curable material that molecular weight is less than 450.
70. methods according to any one of claim 66-69, the heat heating that wherein said printing-ink uses low pressure mercury lamp to produce.
71. methods according to any one of claim 66-70, wherein the UV of low pressure mercury lamp irradiates the peak wavelength with about 254nm.
72. purposes of equipment in the method as described in any one of claim 48-64 as described in any one of claim 29-50.
73. purposes of equipment in the method as described in any one of claim 66-71 as described in any one of claim 44-50.
CN201080045759.1A 2009-08-21 2010-08-20 Printing ink, apparatus and method Pending CN104220537A (en)

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GB0914648.1 2009-08-21
GB0914648A GB0914648D0 (en) 2009-08-21 2009-08-21 Printing apparatus
GB0914652.3 2009-08-21
GB0914652A GB0914652D0 (en) 2009-08-21 2009-08-21 Printing ink
GB0920271A GB0920271D0 (en) 2009-11-19 2009-11-19 Printing ink
GB0920271.4 2009-11-19
PCT/GB2010/051384 WO2011021052A2 (en) 2009-08-21 2010-08-20 Printing ink, apparatus and method

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